Nickel plating solutions



V r 3,000,799 NICKEL PLATING SOLUTIONS Jack L. Towle, Cleveland, Ohio, assignor to The Harshaw GheinitEal Gompany, Cleveland, Ohio, a corporatihn Qf h a... H

No Drawing, Eiled Feb; ,10,,1 9 60, $er. No. 7,783

12 Claims. (Cl. 204- 49) This invention, which is a continuation-in-part 6f espending applicatio'rl Serial No. 833,398, filed August 13; 1959 now abandoned, which is a continuation-in-part of copending application Serial No. 796,211, filed March 2, 1959 now abandoned, relates to electrodeposition of bright nickel, that is, to the production or bright deposits of nickel which are bright as taken from the electroplating solution without bufiing or polishing of any kind, and to the composition of solutins suitable for the pi'dduetion of such deposits.

Various solutions are known which are capable of pro= dueing bright nickel deposits. Some of these are 65 com mercial value. Some are superior in pa'rticularrespets while being inferior in other respects. Brightness, resistance to corrosion, long periods of trouble-free operation, adherence, ductility, freedorii from pits, streaks and other irregularities, resistance to impurities in the bath are some of the factors which the art seeks to find in high degree angles many as possible in one process.

I have newdiscovered a group oi closely related classes of compounds comprised within the general formula below which are excellent additives for use in acid nickel plating when used in connection with the aromatic sulfonates, sulfonarnides and suliiinide's. The latter may be referred to as control agents, the for-i'ner as brighteners or auxiliary brighteners. I

The biifg'h'teii'ef's with whih the invention i cs'neeraea are thds'e having the teams M M wherein n is an integer from 1 to 6, n is an integer from 1 to 6, R is a member selected from the group consisting of where R" and R' are independently selected earn the group consisting of hydrocarbon radicals and hydrogen; R is a member selected from the group consisting of where m is an integer from 1 to 6,

United States Patent "ice where R" and R' are independently selected from the group consisting of hydrocarbon radicals and hydrogen; W is a hydrocarbon radicalrX is an acidic radical selected from the group consisting 6f sulfate, sulfonate, halide and perchlorate radicals and t is an integer from 0 to 1 inclusive. M

The classes of brighteners referred to are as follows:

H -woman where n is 2 and the hydrogen atoms may be substituted by methyl and where W is a hydrocarbon radical, X is acidic radical selected from the group consisting of sul fate, sulfonate, halide and perchlorate radicals and t is integer from 0 to 1 inclhsive.

(WM 35); where R is a hyzi aearbea iadieal having item 1 to a: 1561i areas, it is {2 and the hydrogen atom iiiay as sub} stitu'ted by methyl, and where W is a hyaraearbeh radii-:51, X is an acidic radical selected from the roup consisting oi sulfate; sulfonate, halide and perchlorate radi'als; ai'id t is an integer from 0 to 1 inclusive.

(3) [CHs0-(CHa)n]2S where n is 2, and whre W is a hydrocarbon radical, X is an acidic radical selected from the group consisting of sulfate, sulfonate halide and perchlorate radicals, and r is an integer from 0 to 1 inclusive.

son s-m s oein -(sheaths where R and R are members independently selected from the group consisting of H and CH n is an integer from 1 to 3, and m is a n integer from 1 to 2, and where W id a hydrocarbon radical, X is an acidic radical selected from the group consistiiig of sulfate, sulfonate, halide and perchlorate radicals, and t is an integer from 0 to 1 ill.- clusive.

where is an integer from '1 to '3' and is an integer ffom 1 to 3, and Where W is a hydrocarbon radical, X is an acidic radieal selected from the group consisting of sulfate, sulfonate, halide and perchlorate radieals, and t is an integer frdiii 0 to 1 inclusive.

bdn atoms, and n is 2, and where Wis a hydrocarbon radical, X is an acidic radical selected from the group consisting of sulfate, sulfonate, halide and perchlorate radicals, and t is an integer from to 1 inclusive.

where R is a hydrocarbon radical having from 1 to 6 carbon atoms and n is an integer from 1 to 2, and where W is a hydrocarbon radical, X is an acidic radical selected from the group consisting of sulfate, sulfonate, halide and v perchlorate radicals, and tis an integer from '0 to. 1- inclusive. s

oi fi where R is a'hy focarbonfiradical havinggfrom i1: to'-6 carbon atoms and n is an integer from 1 to 2,. and where Wis a hydrocarbon radical, X is an acidic radical selected from the group consisting of sulfate, sulfonate, halide and perchlorate radicals, and t is an integer from 0 to 1-. inclusive.

u c. r

where n is an integer from 1 to 2, and where W is a hydrocarbon radical, X is' an acidicradi'cal selected from the group consisting of sulfate, sulfonate, halide and perchlorate radicals, and t is an integer from 0. to .1 inclusive.

where n is an integer from 1 to 2, and where W is a hydrocarbonradioal, X is an acidic radical selected from the group consisting of sulfate, sulfonate, halide and perchlorate radicals, and t is an integer from 0 to l inelusive,

a-tcmn-p (wk i where R is a'hydrocarbon radical having from 1 to 12 carbon atoms and n is 2, and where W is a hydrocarbon radicaL'X is an acidic radical selected from the group consisting of-vsulfate, sulfonate, halide and perchlorate radicals, ancltv is an integer fromO to l inclusive. j H

' v cameraman (W): (X): I where n is 2, and where W is a hydrocarbon radical, X is an acidic radical selected from 'the group consisting of sulfate-emanate, halide and perchlorate radicals, and t is an integer from 0 to 1 inclusive. 1 (is g P H R-S(CHz)nGNHz .Y (Kn where R is a hydrocarbon radical having from 1 to carbon atoms and n is 2, and where W is a hydrocarbon radical, X is an acidic radical selected from the group consisting of sulfate, sulfonate, halide and perchlorate radicals, and t is an integer from 0 to 1 inclusive.

(16) g suonanornr I g U o where n is 2, and where W is a hydrocarbon radical, X is anacidicradical" selected from the group" consisting'of sulfate, sulfonate, halideandperchlorate radicals ,..and t is an integer from 0 to l inclusive.

(l7) HQCHzCHsSCHzCHaSOnCHzCHzSCHzCHzOH (W): h (WM (X):

where W is a hydrocarbon radical, X is an acidic radical selected from the group consisting of sulfate, sulfonate, halide and perchlorate, and t is an integer from 0 to 1 inclusive.

The foregoing brighteners may be employed in the bright acid nickel plating solution at the rate. of 0.0025 to 0.075 gram per liter.

Specific examples of brightener compositions according to the invention are set forth in Table I below. 1

. TABLE 1' Preferred No. Structure 1 Name Concentrait tion, Grams per Liter N N 1. l, 5-Bi's(2'-benzlmidazolyl)-3-thiapantane, 0. 01-11015 or BlslB- '-benzimidazolyl) ethyl] sul- C-OHaCHrB-GHaCHz-C fide.

\ N E H 7 The Second addition agent, which cooiirats Withthe brightener in bright, acid, nickel plating soljitions falls into the category of organic siilfonamides', sulfir'nid, and suifonates'. 35

I The amount of control agent dissolved in the acid nickel filat ing solution ranges from ,05 gram per liter to 2 0 grarhs per liter, best results being obtained from about 2 to about 5 grams per liter. These may be used in admixture as Wellas singly. That is, two control agents may be ris'ed 70 instead of one, their combined concentration being kept within the above indicatedlirnits n It is to be understood that in the case qt the suifonium compounds, the radicalcorresponding to X iiithe general maon page 1 may be writtenas carrying a negative 75 I charge while the remainder f the ear-1 106006 me Be written as carrying a positive charge, a v. aqcmon sacm n' W X or as written in column 1, lines 38 00a 39.

TABLE IT Aromatic sulfonamides benzene monosul fonai'riide C 'H SO NH eh'at n smfiuin. Sall- C H S0 GQNNa Table IlContinued p-toluenesulfonamide I cnt c n so rln trichlorodibenzene'sulfonamide Cl C I-I SO NHSO C I-I Cl M dii-naphthalenesulfonamide o n so Nnso c rn 4-carboxydibenzenesulfonamide C H SO NHSO C H COOH 1 p,p'-methylene-bis(dibenzenesulfonamide) c n so nnso c nncn cnns0,,1-1ns0,c,n

Aromatic sulfonates benzene monosulfonic acid C H SO H benzene disulfonic acid s 4( 3 2 nickel naphthalene disulfonate 1o a( 2 s cobalt naphthalene disulfonate (CSHBSOQZCO I nickel benezene monosulfonate s 5 s)z dichlorobenezene disulionic acid 2 s 2( s 2 r f toluene sulfonic acid cn c n so n diphenyl sulfonic acid C H C H SO H 'thiophene sulionic acid C4H3S.SO3H

, diphenyl sulfone s s z s s naphthalene trisulfonic acid sodium allyl sulfonate H C= CHCH SO Na vinyl sulfonamide H O: CHSO NH The constitutents of the plating bath, according to the preferred practice of the invention, are (1) water, (2) nickel sulfate, nickel chloride, or a mixture of nickel sulfate and. nickel, chloride,. (3) the brightcner, (4) a sulfouate, a sulfonamide, a sulfimide, or one or more sulfonates, sulfonamides, sulfirnides or mixtures thereof of the type previously indicated, (5) and a wetting agent (optional). An additional ingredient of the solution which is desirable is a bufi'ering agent such as boric acid, formic acid, or the like.

It will be noted that in reference to the major constituent of the nickel plating solution, the solutions are similar to the wellknown "all chloride, all sulfate, and "sulfate-chloride" or Watts type acid nickel plating solutions. The essential novel feature of the invention is the use of an acid nickel plating solution having one or more nickel electrolytes selected from nickel sulfate and nickel chloride and additionally containing cooperating brightening agents, one of which is at least one carrier selected from the group consisting of unsaturated aliphatic sulfonamides, unsaturated aliphatic sulfimides,""uns'a'tu= without eliminating pitting.

rated aliphaticsulfonates, aromatic sulfonamides, ,aromatic sulfimides and aromatic sulfonates, and the other of which is a small amount of a brightener of the type heretofore indicated.

The basic solutions in connection with which the bright ductile nickcldeposits are realized when containing the cooperating addition agents dissolved therein are as follows: ALL SULFATE NlSO4.7HaO to 400 grams, preferably 200 to 300 grams.

Boric acid 0 to 60 grams, preferably 1010 40 grams. Wetting agent (e.g. sodium lauryl sulfate) 0 to 0.5 gram, preferably 0.05

to 0.2 gram. H20 to make 1000 cc.

ALL CHLORIDE NiChBHzO 50 to 250 grams, preferably 100 to 200 grams. Boric acid-.. O to 60 grams, preferably 10 to 40 grams. Wetting1 agent (e.g. sodium laury sulfate) 0 to 0.5 gram, preferably 0.05

to 0.2 gram H20 to make 1000 cc.

SULFATE-CHLORIDE WATTS TYPE NISOa-THaO L. 100 to 400 grams, preferably 200 to 300 grams. N1Cla.6HzO 10 60 grams, preferably 25 to grams. Boric acid 0 to 50 grams, preferably 15 to 40 grams.

Wetting agent (e.g. sodium laury1su1fate). r. 0 to 0.5 gram, preferably 0.025

; to 0.2 gram. Hi0 to make 1000 cc.

The plating solutions above identified may be operated under conditions of pH, temperature, and cathode current density which are customarily employed therewith. When the cooperating brightening agents of the invention are dissolved in the plating solutions in the amount previously indicated, bright, ductile deposits will be obtained upon electrolysis of the solution. Typical operating conditions for the basic solutions are as follows:

' All Sulfate All Chloride Watts n 3-4. 5 2.4-4. 5 3-4.5 emperature o r 120-160 100-150 -100 Cathode Current Density 7 (amp/it!) 20-40 00-200 30-10 In thepreparation of the plating solution according to the invention, I add to each of the foregoing basic solutions a suitable quantity of the brightener and also one or more of the unsaturated aliphatic, or aromatic sulfonamides, sulfimides, and sulfonates. The plating solution for the best results, contains an antipitting agent although the deposits may be suitable for some purposes Sodiumlauryl sulfate --or other wetting agents such as the sodium sulfate derivative of 7-ethyl-2-mcthyl-undecanol-4 and the dihexyl ester of sodium sulfosuccinic acid may be used as an antipitting agent, although its use is not essential and other wetting agents or mixtures of wetting agents may be used to control the pitting. For some purposes pitting may betolerated. and sometimes very little pitting occurs.

Specific examples of electroplating solutions containing .difierent cooperating brighteners and carriers are illustrated in the following table which has been designated as Table III. It should be understood that the specific electroplating solution may be employed with or,

is. l -rv' in acid nickel plating processes utilizing solutions of the type indicated herein. Y

What I claim is: 1. An aqueous acid nickel plating solution comprising a source of nickel ions selected from the class consisting of nickel sulfate, nickel chloride and mixtures thereof, said solution also containing cooperating additives for enhancing the brightness of nickel deposits produced therein, one of said additives being chosen from the class consisting-of aromatic sultonates, aromatic sulfonamides, aromatic sulfimides, aliphatic sulfonates and sulfonic acids and the second being chosen from the class of compounds having the formula R*(CH S(CH -R, where n is an integer from 1 to 6, n is an integer from 1 to 6, R is a member selected from the group consisting of IO E, -0H,-0CH5, 'i-n, i--on, -t .i'oonj nn Where m is an integer from 110 6,

R moi-crowns onionion, J-N

. h R' where W is a hydrocarbon radical, X. is an acidic radical selected from the group consisting of sulfate, sulfonate, halide and perchlorate radicals, and t is an integer from O'to 1 inclusive, where R" and R are independently se lected from the group consisting of hydrocarbon radicals and hydrogen; R is a member selected from the group consisting of a 0 II N ll -on, -oon,, -c--n, -o-on *C -Q-(QEQmH a where m is an integer from 1 to 6, p

where R and R are independently selected from the group consisting of hydrocarbon radicals and hydrogen wherein said second mentioned additive is present in solution in concentrations of from 0.0025 to 0.075 gram per liter, and said first mentioned additive being present in solution in concentrations of from 0.05 to 20 grams per liter.

2. An aqueous, acid, nickel plating solution comprising nickel sulfate and nickel chloride and cooperating additives, one of said additives being present in solution in concentrations of from 0.05 to 20 grams per liter, and being chosen from the class consisting of aromatic sulfonates, aromatic sulfonamides, aromatic sulfimides, ali- 1 0 phatic sulfonarnides and sulfonic acids, and the other-oi said cooperating additives being a compound of the formula and being dissolved in said solution in concentration from 0.0025 to 0.075 gram per liter.

3. An aqueous, acid, nickel plating solution comprising nickel sulfate and nickel chloride and cooperating additives, one of said additives being present in solution in concentrations of from 0.05 to 20 grams per liter, and being chosen from the class consisting of aromatic sulfonates, aromatic sulfonarnides, aromatic sulfimides, aliphatic sulfonamides and sulfonic acids, and the other of said cooperating additives being a compound of the formula and being dissolved in said solution in concentration from 0.0025 to 0.075 gram per liter. I

4. An aqueous, acid, nickel plating solution compris ing nickel sulfate and nickel chloride and cooperating additives, one of said additives being present in solution in concentrations'of from 0.05 to 20 grams per liter, and being chosen from the class consisting of aromatic sulfonate's, aromatic sulfonamides, aromatic sulfimides, aliphatic sulfonamides and sulfonic acids, and the other of said cooperating additives being a compound of the formula [CH -O--OH -CH S and being dissolved in said solution in concentration from 0.0025 to 0.075 gram per liter.

5. An aqueous, acid, nickel plating solution compris ingnickel sulfate and nickel chloride and cooperating additives, one of said additives being present in solution in concentrations of from 0.05 to 20 grams per liter, and being chosen from the class consisting of aromatic sulfonates, aromatic sulfonamides, aromatic sulfimides, ali phatic sulfonamides and sulfonic acids, and the other of said cooperating additives being a compound of the formula and'being dissolved in said solution in concentration from 0.0025 to 0.075 gram per liter.

7. An aqueous, acid, nickel plating solution compris= ing nickel sulfate and nickel chloride and cooperating additives, one of said additives being present in solution in concentrations of from 0.05 to 20 grams per liter, and being chosen from the class consisting of aromatic sulfonates, aromatic sulfonamides, aromatic sulfimides, aliphatic sulfonamides and sulfonic acids, and the other of said cooperating additives being a compound of the formula CHaCHzCHzSCH2CHr-t l H and being dissolved in said solution in concentration from 0.0025 to 0.075 gram per liter.

8. An aqueous, acid, nickel plating solution comprising nickel sulfate and nickel chloride and cooperating additives, one of said additives being present in solution in concentrations of from 0.05 to grams per liter, and being chosen from the class consisting of aromatic sulfonates, aromatic sulfonamides, aromatic sulfimides, aliphatic sulfonamides and sulfonic acids, and the other of said cooperating additives being a compound of the formula OHaCHs-S-CHnCH and being dissolved in said solution in concentration from 0.0025 to 0.075 gram per liter.

9. An aqueous, acid, nickel plating solution comprising nickel sulfate and nickel chloride and cooperating additives, one of said additives being present in solution in concentrations of from 0.05 to 20 grams per liter, and being chosen from the class consisting of aromatic sulfonates, aromatic sulfonamides, aromatic sulfimides, aliphatic sulfonamides and sulfonic acids, and the other of said cooperating additives being a compound of the formula and being dissolved in said solution in concentration from 0.0025 to 0.075 gram per liter. 11. An aqueous, acid, nickel plating solution comprising nickel sulfate and nickel chloride and cooperating additives, one of said additives being present in solution in concentrations of from 0.05 to 20 grams per liter, and being chosen from the class consisting of aromatic sulfonates, aromatic sulfonamides, aromatic sulfimides, ali 'phatic sulfonarnides and sulfonic acids and the other of said cooperating additives being a compound of the formula HOCH CH SCH OH SO CI-I CH SCH CH OH and being dissolved in said solution in concentration from 0.0025 to 0.075 gram per liter.

12. An aqueous, acid, nickel plating solution comprising a source of nickel ions selected from the class consisting of nickel sulfate, nickel chloride and mixtures thereof,

ie e-re? ll 1 ll 1 -11, -03, -0oHi, -c-H,- i-orr, C0-(0H:)mH- where m is an integer from 1 to 6,

n (wt a... (.4 a.

O /N N where R" and R" are independently selected from the group consisting of hydrocarbon radicals and hydrogen; R is a member selected from the group consisting of -'0 CH8 O-0H where m is an integer from 1 to 6,

' N/ \N (W0 ix). (wf ix.

where R" and R' are independently selected from the group consisting of hydrocarbon radicals and hydrogen; W is a hydrocarbon radical; X is an acidic radical selected from the group consisting of sulfate, sulfonate, halide and perchlorate radicals and t is an integer from 0 to 1 inclusive wherein said second mentioned additive is present in solution in concentrations of from 0.0025 to 0.075 gram per liter, and said first mentioned additive being present in solution in concentrations of from 0.05 to 20 grams per liter.-

References Cited in the file of this patent UNITED STATES PATENTS Gundel et al. Apr. 8, 1958 Strauss et a1. Oct. 27, 1959 UNITED STATES PATENT OFFICE CERTIFICATION OF CORRECTION Patent No. 3,000 799 September 19 1961 Jack L. Towle It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column l lines 47 to 54, the third formula should appear as shown below instead of as in the patent:

column 2, line 50 for "a n" read an column 4, line 57 after "perchlorate" insert radicals columns 5 and 6 Table I--Continued column 41; line 14 thereof for "0,0lO,Q]5"- read OOl-0,02 column 7, line 31 for "benezene" read benzene line 33., for "dichlorobenezene" read dichlorobenzene column 12, lines 8 and 9, the formula should appear as shown below instead of as in the patent:

Signed and sealed this 27th day of March 1962.

(SEAL) Attest:

ERNEST w. SWIDER DAVID L. LADfl Attesting Officer Y Commissioner of Patents Attest: 

1. AN AQUEOUS ACID NICKEL PLATING SOLUTION COMPRISING A SOURCE OF NICKEL IONS SELECTED FROM THE CLASS CONSISTING OF NICKEL SULFATE, NICKEL CHLORIDE AND MIXTURES THEREOF, SAID SOLUTION ALSO CONTAINING COOPERATING ADDITIVES FOR ENHANCING THE BRIGHTNESS OF NICKEL DEPOSITS PRODUCED THEREIN, ONE OF SAID ADDITIVES BEING CHOSEN FROM THE CLASS CONSISTING OF AROMATIC SULFONATES, AROMATIC CULFONAMIDES, AROMATIC SULFIMIDES, ALIPHATIC SULFONATES AND SULFONIC ACIDS AND THE SECOND BEING CHOSEN FROM THE CLASS OF COMPOUNDS HAVING THE FORMULA R$-(CH2)N''-S(CH2)N-R'', WHERE N IS AN INTEGER FROM 1 TO 6, N'' IS AN INTEGER FROM 1 TO 6, R IS A MEMBER SELECTED FROM THE GROUP CONSISTING OF 